[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP2256236A1 - Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren - Google Patents

Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren Download PDF

Info

Publication number
EP2256236A1
EP2256236A1 EP10163360A EP10163360A EP2256236A1 EP 2256236 A1 EP2256236 A1 EP 2256236A1 EP 10163360 A EP10163360 A EP 10163360A EP 10163360 A EP10163360 A EP 10163360A EP 2256236 A1 EP2256236 A1 EP 2256236A1
Authority
EP
European Patent Office
Prior art keywords
nanotubes
fiber
conductive composite
fibers
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10163360A
Other languages
English (en)
French (fr)
Inventor
Patrice Gaillard
Philippe Poulin
Célia Mercadier
Maryse Maugey
Sandy Moisan
Alain Derre
Cécile ZAKRI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Arkema France SA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2256236A1 publication Critical patent/EP2256236A1/de
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals

Definitions

  • the present invention relates to a process for obtaining conductive composite fibers based on homo- or copolymer of vinyl alcohol with a high content of nanotubes capable of providing thermal and / or electrical conduction, in particular of carbon nanotubes. It also relates to the conductive composite fibers obtainable by this method, as well as their uses.
  • Carbon nanotubes are known and possess particular crystalline structures, tubular, hollow and closed, composed of atoms arranged regularly in pentagons, hexagons and / or heptagons, obtained from carbon.
  • CNTs generally consist of one or more graphite sheets wound coaxially.
  • SWNTs single wall nanotubes
  • Multi Wall Nanotubes or MWNTs Multi Wall Nanotubes
  • CNTs have many powerful properties, namely electrical, thermal, chemical and mechanical.
  • composite materials intended in particular for the automotive, nautical and aeronautical industries, electromechanical actuators, cables, resistant wires, chemical detectors, energy storage and conversion, electron emission displays, electronic components, and functional textiles.
  • conductive such as NTCs allow the heat and electrical dissipation of heat and electric charges arising during friction.
  • the CNTs when synthesized, are in the form of a disorganized powder, consisting of entangled filaments, which makes them difficult to implement in order to exploit their properties. In particular, to exploit their mechanical and / or electrical properties on a macroscopic scale, it is necessary for the CNTs to be present in large quantities and oriented in a preferred direction.
  • Another approach for producing CNT-loaded polymer fibers is to mix the nanotubes and a polymer in the same solution before spinning.
  • the solution thus produced is then injected into a static bath or in a flow which induces the coagulation of the polymer.
  • the nanotubes mixed with the polymer are trapped in the structure and the final object is a composite fiber loaded with carbon nanotubes.
  • the advantage of this principle is that it relies on the coagulation of the polymer and not directly on the coagulation of the nanotubes. Coagulation of the polymer allows consolidated fibers to be obtained more rapidly which can be easily handled and extracted from the coagulation baths to be, for example, washed, dried, drawn and wound.
  • the spinning of polymer fibers by solvent coagulation and their treatments are well described in the literature.
  • the fibers described by Zhang et al. contain a mass fraction of not more than 3% of carbon nanotubes.
  • process according to the invention may optionally comprise other preliminary, intermediate and / or subsequent stages to those mentioned above, provided that these do not adversely affect the formation of the conductive composite fiber. .
  • fiber is meant, within the meaning of the present invention, a strand whose diameter is between 100 nm (nanometers) and 300 microns (micrometers), preferably between 1 and 100 microns (micrometers), better, between 2 and 50 ⁇ m (micrometers).
  • This structure may also be porous or non-porous.
  • a fiber is intended to ensure the holding of a mechanical part and does not constitute a tube or pipe for the transport of a fluid.
  • the nanotubes consist of at least one chemical element chosen from the elements of columns IIIa, IVa and Va of the periodic table.
  • the nanotubes must be capable of providing thermal and / or electrical conduction; they can thus be based on boron, carbon, nitrogen, phosphorus or silicon.
  • they may be constituted or contain carbon, carbon nitride, nitride of boron, boron carbide, boron phosphide, phosphorus nitride or carbon boronitride, or silicon.
  • carbon nanotubes are used. These are graphitic carbon fibrils, hollow, each having one or more graphitic tubular walls oriented along the axis of the fibril.
  • the nanotubes usually have a mean diameter ranging from 0.1 to 100 nm (nanometers), more preferably from 0.4 to 50 nm (nanometers) and better still from 1 to 30 nm (nanometers) and advantageously a length of 0, 1 to 10 ⁇ m (micrometers).
  • Their length / diameter ratio is preferably greater than 10 and most often greater than 100 or even greater than 1000.
  • Their specific surface area is, for example, between 100 and 500 m 2 / g (including limits), generally between 100 and 300 m 2.
  • the multiwall nanotubes may for example comprise from 5 to 15 sheets (or walls) and more preferably from 7 to 10 sheets. These nanotubes can be treated or not.
  • Carbon nanotubes are commercially available or can be prepared by known methods.
  • An example of crude carbon nanotubes is especially commercially available from the company Arkema France under the trade name Graphistrength® ® C100.
  • Hyperion Catalysis International Inc. describes the synthesis of carbon nanotubes. More particularly, the process comprises contacting a metal-based particle such as, in particular, iron, cobalt or nickel, with a gaseous compound based on carbon, at a temperature of between 850 ° C. and 1200 ° C. C, the dry weight proportion of the carbon-based compound relative to the metal-based particle being at least about 100: 1.
  • a metal-based particle such as, in particular, iron, cobalt or nickel
  • nanotubes may be, optionally and optionally in combination, purified, treated (for example oxidized) and / or milled before being used in the process according to the invention.
  • the grinding of the nanotubes may in particular be carried out cold or hot and be carried out according to the known techniques used in devices such as ball mills, hammers, grinders, knives, jet gas or any other system grinding capable of reducing the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet grinding technique and in particular in an air jet mill, or in a ball mill.
  • the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities originating from their preparation process.
  • the weight ratio of the nanotubes to the sulfuric acid may especially be between 1: 2 and 1: 3 (limits included).
  • the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C, for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
  • the purification may also consist of a heat treatment at high temperature, typically greater than 1000 ° C.
  • the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
  • the oxidation is advantageously carried out at a temperature below 60 ° C. and preferably at room temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration and / or centrifugation, washing and drying steps of the oxidized nanotubes.
  • the nanotubes In order to eliminate the catalyst metal residues, it is also possible to subject the nanotubes to a heat treatment of at least 1000 ° C., for example 1200 ° C.
  • the first step of the process according to the invention consists in forming a dispersion of nanotubes in a solution of homo- or copolymer of vinyl alcohol, in the presence of at least one stabilizing agent covalently or non-covalently bonded to the nanotubes.
  • the homo- or copolymer of vinyl alcohol is the polyvinyl alcohol itself.
  • its molecular weight may be between 5,000 and 300,000 g / mol. Its degree of hydrolysis may be greater than 96%, or even greater than 99%.
  • the term "stabilizing agent” is intended to mean a compound that allows homogeneous dispersion of the nanotubes in the solution, which protects the nanotubes from coagulation in the presence of the homo- or copolymer of vinyl alcohol, but which does not interfere with the coagulation of the homo- or copolymer of vinyl alcohol in a coagulation solution.
  • the stabilizing agent (s) according to the invention are bonded to the nanotubes either covalently or non-covalently.
  • the stabilizing agent is non-covalently bonded to the nanotubes, it may be chosen from essentially nonionic surfactants.
  • the term "essentially nonionic surfactant” is intended to mean a nonionic amphiphilic compound, cited for example in McCutcheon's 2008 "Emulsifiers and Detergents", and preferably having an HLB (hydrophilic-lipophilic balance). from 13 to 16, as well as block copolymers containing hydrophilic blocks and lipophilic blocks and having a low ionicity, for example 0% to 10% by weight of ionic monomer and 90% to 100% of nonionic monomer.
  • HLB hydrophilic-lipophilic balance
  • the stabilizing agent is covalently bonded to the nanotubes
  • it is preferably a hydrophilic group, preferably a polyethylene glycol group grafted onto the nanotubes.
  • the grafting of reactive units such as polyethylene glycol groups on the surface of the nanotubes can be carried out according to any method known to those skilled in the art.
  • the person skilled in the art may relate to the publication of B. Zhao et al. (Synthesis and Characterization of Water Soluble Single-Walled Carbon Nanotube Graft Copolymers, J. Am Chem Soc. (2005) Vol 127 No 22 ).
  • the nanotubes are dispersed in dimethylformamide (DMF) and are contacted with oxalyl chloride.
  • DMF dimethylformamide
  • PEG polyethylene glycol
  • the nanotubes thus grafted are purified.
  • the dispersion produced in the first step of the process according to the invention comprises a solvent which is preferably chosen from water, dimethylsulfoxide (DMSO), glycerol, ethylene glycol, diethylene glycol and triethylene glycol. , diethylene triamine, ethylene diamine, phenol, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and mixtures thereof.
  • a solvent which is preferably chosen from water, dimethylsulfoxide (DMSO), glycerol, ethylene glycol, diethylene glycol and triethylene glycol. , diethylene triamine, ethylene diamine, phenol, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone and mixtures thereof.
  • the solvent is chosen from water, DMSO and mixtures thereof in all proportions.
  • the pH of the aqueous dispersion can be maintained preferably between 3 and 5 by addition of one or more acids, which can be chosen from inorganic acids, such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as acetic acid, tartaric acid and oxalic acid and mixtures of organic acid and organic acid salt such as acid citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate.
  • inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid
  • organic acids such as acetic acid, tartaric acid and oxalic acid and mixtures of organic acid and organic acid salt such as acid citric acid and sodium citrate, acetic acid and sodium acetate, tartaric acid and potassium tartrate, tartaric acid and sodium citrate.
  • the dispersion may comprise boric acid, borate salts, or mixtures thereof.
  • the dispersion may also comprise a salt selected from zinc chloride, sodium thiocyanate, calcium chloride, aluminum chloride, lithium chloride, rhodanates and mixtures thereof. They make it possible to optimize the rheological properties of the dispersion and to promote the formation of the fiber.
  • the dispersion is carried out by means of ultrasound or a rotor-stator system or a ball mill. It can be carried out at room temperature, or by heating, for example, between 40 and 120 ° C.
  • the dispersion thus produced during the first step of the process according to the invention may comprise from 2% to 30% by weight of homo- or copolymers of vinyl alcohol, from 0.1% to 5% of nanotubes, from 0.1% to 5% of stabilizing agent, relative to the total mass of the dispersion, including the solvent.
  • the second step of the process consists in injecting said dispersion obtained during the first step into a coagulation solution to form a pre-fiber, in the form of monofilament or multi-filaments.
  • coagulation solution means a solution which causes the homo- or copolymer of vinyl alcohol to solidify.
  • the coagulation solution comprises a solvent chosen from water, an alcohol, a polyol, a ketone and their mixtures, more preferably a solvent chosen from water, methanol, ethanol, butanol, propanol, isopropanol, glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene and mixtures thereof, and even more preferably a solvent selected from water, methanol, ethanol, a glycol acetone and their mixtures.
  • a solvent chosen from water, an alcohol, a polyol, a ketone and their mixtures more preferably a solvent chosen from water, methanol, ethanol, butanol, propanol, isopropanol, glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene and mixtures thereof, and even more preferably a solvent
  • the coagulation solution advantageously has a temperature of between 10 and 80 ° C. If the solvent of the coagulation solution is essentially organic, such as methanol, the coagulation solution advantageously has a temperature between -30 and 10 ° C.
  • the coagulation solution may comprise one or more salts intended to promote the coagulation of the homo- or copolymer of vinyl alcohol, chosen from alkaline salts or desiccant salts such as ammonium sulphate, sulphate of potassium, sodium sulfate, sodium carbonate, sodium hydroxide, potassium hydroxide and mixtures thereof.
  • alkaline salts or desiccant salts such as ammonium sulphate, sulphate of potassium, sodium sulfate, sodium carbonate, sodium hydroxide, potassium hydroxide and mixtures thereof.
  • the coagulation solution may comprise one or more additional compounds which are intended to improve the mechanical properties, the water resistance of the fiber and / or facilitate the spinning of the fiber.
  • the coagulation solution may therefore comprise at least one compound selected from boric acid, borate salts and mixtures thereof.
  • the coagulation solution is saturated with salts.
  • the dispersion is injected during the second step of the process according to the invention through one or a set of needles and / or one or a set of nonporous cylindrical or conical nozzles into the coagulation solution, which can be static (static bath) or in motion (flow).
  • the average injection speed of the dispersion may be between 0.1 m / min and 50 m / min, preferably between 0.5 m / min and 20 m / min.
  • the coagulant solution induces coagulation in the form of a pre-fiber by solidification of the homo- or copolymer of vinyl alcohol.
  • the nanotubes are trapped in the polymer that solidifies.
  • the next step of the process according to the invention consists in extracting, continuously or not, the pre-fiber from the coagulation solution.
  • the wash tank preferably includes water.
  • the washing step can eliminate a portion of the peripheral polymer of the pre-fiber and thus enrich (up to 70% by weight) the composition of the pre-fiber into nanotubes.
  • the washing bath may comprise agents which make it possible to modify the composition of the pre-fiber or which chemically interact with it.
  • chemical or physical crosslinking agents in particular borate salts or dialdehydes, may be added to the bath to reinforce the pre-fiber.
  • the washing step can also make it possible to eliminate the agents, in particular the surfactants, potentially detrimental to the mechanical or electrical properties of the fiber.
  • a drying step is also included in the process according to the invention. This step can take place either directly after extraction or after washing. In particular, if it is desired to obtain a polymer-enriched fiber, it is desirable to dry the pre-fiber directly after the extraction.
  • the drying is preferably carried out in an oven that will dry the pre-fiber through a gas flowing in an interior duct of the oven. The drying can also be carried out by infrared radiation.
  • the method according to the invention may also comprise a winding step, and optionally a hot stretching step performed between the drying step and the winding step. It may also include stretching in solvents at different times.
  • This stretching step may be carried out at a temperature above the glass transition temperature (Tg) of the homo- or copolymer of vinyl alcohol and preferably below its melting point (if it exists).
  • Tg glass transition temperature
  • Such a step, described in the patent US 6,331,265 enables the nanotubes and the polymer to be oriented substantially in the same direction, along the axis of the fiber, and thus to improve the mechanical properties of the latter, in particular its Young's modulus and its rupture threshold.
  • the draw ratio defined as the ratio of the length of the fiber after drawing to its length before drawing, may be between 1 and 20, preferably between 1 and 10, included. Stretching can be done in one go, or several times, allowing the fiber to relax slightly between each stretch.
  • This stretching step is preferably conducted by passing the fibers through a series of rolls having different rotational speeds, those which unroll the fiber rotating at a lower speed than those receiving it.
  • the fibers may be passed through ovens arranged between the rolls, or heated rollers may be used, or these two techniques may be combined. This stretching step makes it possible to consolidate the fiber and to achieve high breaking point stresses.
  • Another subject of the present invention is the conductive composite fibers that can be obtained according to the method of the invention.
  • Said conductive composite fibers obtained are characterized in that they contain from 5 to 70% by weight of nanotubes, preferably from 5 to 50%, more preferably from 5 to 30%, and more preferably from 5 to 25%, by in relation to the total weight of the fibers. It is therefore possible to obtain composite fibers with a high content of nanotubes.
  • the conductive composite fibers obtained according to this process have a resistivity which can be between 10 -3 and 10 5 ohm.cm at room temperature. This electrical conductivity can be further improved by heat treatments.
  • the manufacture of these composite parts can be carried out according to various processes, generally involving a step of impregnating the composite fibers.
  • conductive according to the invention by a polymeric composition containing at least one thermoplastic material, elastomeric or thermosetting.
  • This impregnation step may itself be carried out according to various techniques, depending in particular on the physical form of the polymeric composition used (pulverulent or more or less liquid).
  • the impregnation of the conductive composite fibers is preferably carried out according to a fluidized bed impregnation process, in which the polymeric composition is in the form of powder. Pre-impregnated fibers are thus obtained.
  • preimpregnated fiber fabrics of identical or different composition, can be stacked to form a plate or a laminated material, or alternatively subjected to a thermoforming process.
  • the pre-impregnated fibers may be combined to form ribbons which may be used in a filament winding process which makes it possible to obtain hollow pieces of almost unlimited shape, by winding the ribbons on a mandrel having the shape of the part to be made.
  • the manufacture of the finished part comprises a step of consolidating the polymeric composition, which is for example melted locally to create zones for fixing the fibers pre-impregnated with each other and / or to secure the fiber ribbons pre-impregnated with each other. impregnated in the filament winding process.
  • a film from the polymeric impregnating composition in particular by means of an extrusion or calendering process, said film having for example a thickness of about 100 ⁇ m, then of placing it between two conductive composite fiber mats according to the invention, the assembly then being hot pressed to allow the impregnation of the fibers and the manufacture of the composite part.
  • the present invention thus has for another object composite materials comprising conductive composite fibers according to the invention, bonded together by weaving or by a polymeric composition.
  • the dispersion was then injected into a static bath of a saturated sodium sulfate coagulant solution (320 g / L) at 40 ° C.
  • the pre-fiber was extracted from the coagulation bath after a residence time of less than ten seconds. It was then dried by infra-red radiation, then redirected into a washing bath containing water. After 1 min, it was dried again by infrared radiation and then wound.
  • the final fiber obtained contains 8% of nanotubes in mass. This value was obtained by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the fiber is cylindrical and homogeneous and has been mechanically characterized by traction. It has a breaking energy of 475 J / g, an elongation at break of 425% stretching and a Young's modulus of 3 GPa. After hot stretching at 200 ° C of 400%, its Young's modulus increases to 29 GPa and its rupture threshold increases to 12% stretching.
  • Composite fibers were made starting from aqueous dispersions of multiwall nanotubes. 0.9% by weight of nanotubes and 1.2% Brij®78 were dispersed in water. By the same method as described in Example 1, fibers loaded with 17% multiwall nanotubes were obtained.
  • These fibers have the advantage of combining good mechanical properties with quite interesting electrical properties, since they are electrically conductive, with a resistivity of 10 ⁇ .cm. They have a toughness of 340 MPa, a Young's modulus of 5.5 GPa and an elongation at break of 240%.
  • the solution was then injected into a static bath of a saturated sodium sulfate coagulant solution (320 g / L) at 40 ° C to form a fiber.
  • the final fiber obtained contains 12% of nanotubes in mass. It has a toughness of 360 MPa, a Young's modulus of 4 GPa and an elongation at break of 325%, as well as a resistivity of 30 ⁇ .cm.
  • Example 3 The dispersion described in Example 3 was injected into a coagulant bath containing sodium hydroxide (50 g / L) and sodium sulfate (300 g / L) at 40 ° C.
  • the final fiber obtained contains 12% of nanotubes in mass. It has a toughness of 320 MPa, a Young's modulus of 7 GPa and an elongation at break of 200%, as well as a resistivity of 100 ⁇ .cm.
  • the dispersion was then injected into a methanol coagulant bath at -20 ° C containing 10% DMSO to form 8% nanotube filled fibers.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Inorganic Fibers (AREA)
EP10163360A 2009-05-27 2010-05-20 Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren Withdrawn EP2256236A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0953508A FR2946177B1 (fr) 2009-05-27 2009-05-27 Procede de fabrication de fibres composites conductrices a haute teneur en nanotubes.

Publications (1)

Publication Number Publication Date
EP2256236A1 true EP2256236A1 (de) 2010-12-01

Family

ID=41396371

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10163360A Withdrawn EP2256236A1 (de) 2009-05-27 2010-05-20 Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren

Country Status (7)

Country Link
US (1) US20110017957A1 (de)
EP (1) EP2256236A1 (de)
JP (1) JP2010281024A (de)
CN (1) CN101899723A (de)
FR (1) FR2946177B1 (de)
TW (1) TW201111569A (de)
WO (1) WO2010136704A1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012160288A1 (fr) 2011-05-23 2012-11-29 Arkema France Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
WO2013011250A1 (fr) * 2011-07-21 2013-01-24 Arkema France Fibres composites conductrices a base de graphene
FR2983850A1 (fr) * 2011-12-09 2013-06-14 Commissariat Energie Atomique Procede de fabrication de fibres crues et cuites a base de ceramique(s)
CN105297239A (zh) * 2015-09-17 2016-02-03 无锡市长安曙光手套厂 一种释香织物及其制备方法
CN109502570A (zh) * 2018-12-14 2019-03-22 郑州大学 导电的大应变碳纳米管复合薄膜、制备方法及测试方法

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9242897B2 (en) * 2009-05-18 2016-01-26 Ppg Industries Ohio, Inc. Aqueous dispersions and methods of making same
KR101182380B1 (ko) 2011-03-15 2012-09-12 한양대학교 산학협력단 그라핀 및 탄소나노튜브를 포함하는 하이브리드 고분자 복합 섬유 및 이의 제조 방법
RU2621102C2 (ru) * 2011-09-07 2017-05-31 Коньяр БВ Углеродное нанотрубчатое волокно, имеющее низкое удельное сопротивление
JP5919018B2 (ja) * 2012-02-13 2016-05-18 ニッタ株式会社 カーボンナノチューブを含有するビニロン繊維およびその製造方法
US8739743B2 (en) * 2012-03-27 2014-06-03 Go Green Hybrid Fuel Systems Hydrogen feed method and systems for engines
FR2998573B1 (fr) * 2012-11-26 2015-09-04 Arkema France Melange maitre a base de nanocharges carbonees et de superplastifiant, et son utilisation dans des systemes inorganiques durcissables
KR101946318B1 (ko) 2013-06-19 2019-02-11 코오롱인더스트리 주식회사 공중합 아라미드 섬유의 제조방법 및 이로 제조된 공중합 아라미드 섬유
FR3007412B1 (fr) 2013-06-20 2015-07-17 Centre Nat Rech Scient Procede de recuperation de fibres organiques a partir d'un materiau composite
FR3019563B1 (fr) * 2014-04-03 2016-04-29 Centre Nat Rech Scient Procede de preparation de fibres macroscopiques de dioxyde de titane par extrusion unidirectionnelle continue, fibres obtenues et applications
JP6442160B2 (ja) * 2014-05-09 2018-12-19 日本ゼオン株式会社 カーボンナノチューブ複合材料の製造方法
CN104940989A (zh) * 2015-06-24 2015-09-30 苏州乔纳森新材料科技有限公司 一种可吸收缝合线及其制备方法
CN105220455A (zh) * 2015-09-17 2016-01-06 无锡市长安曙光手套厂 一种香橙味释香织物及其制备方法
CN105133312A (zh) * 2015-09-17 2015-12-09 无锡市长安曙光手套厂 一种驱蚊织物及其制备方法
US10807342B2 (en) * 2015-12-15 2020-10-20 Agc Chemicals Americas, Inc. Layered tube and layer for use in same
CN107299444A (zh) * 2017-06-29 2017-10-27 顾渊 一种释香织物及其制备方法
WO2019086982A1 (en) * 2017-11-06 2019-05-09 King Abdullah University Of Science And Technology Method and device for making copolymer-wrapped nanotube fibers
RU2708583C1 (ru) * 2019-04-12 2019-12-09 МСД Текнолоджис С.а.р.л. Способ получения высокопрочного композиционного материала на основе термопластичного полимера, модификатор для приготовления композиционного материала и способ получения модификатора для приготовления композиционного материала (варианты)
TWI715381B (zh) * 2019-12-27 2021-01-01 穩得實業股份有限公司 纖維級導電高分子組成物及複絲纖維紗線
CN113186656A (zh) * 2021-04-29 2021-07-30 北京石油化工学院 一种氮化碳-聚乙烯醇复合抗菌膜及其制备方法与应用
KR102652781B1 (ko) * 2021-11-01 2024-03-29 한국생산기술연구원 탄소 재료를 포함하는 전도성 섬유 및 그 제조 방법

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850901A (en) 1969-11-25 1974-11-26 T Kimura Polyvinyl alcohol fibers
US3852402A (en) 1969-11-25 1974-12-03 S Tanaka Process for the preparation of polyvinyl alcohol fibers
WO1986003455A1 (en) 1984-12-06 1986-06-19 Hyperion Catalysis International, Inc. Carbon fibrils, method for producing same, and compositions containing same
US4603083A (en) 1983-12-12 1986-07-29 Toray Industries, Inc. Ultra-high-tenacity polyvinyl alcohol fiber and process for producing same
US4612157A (en) 1984-01-31 1986-09-16 Kuraray Company, Limited Method for production of high-tenacity, fine-denier polyvinyl alcohol fiber
EP0395048A2 (de) * 1989-04-27 1990-10-31 Kuraray Co., Ltd. Polyvinylalkoholfaser und Verfahren zu deren Herstellung
US4971861A (en) 1986-12-27 1990-11-20 Unitika Ltd. Polyvinyl alcohol fiber and method of manufacture thereof
US5208104A (en) 1988-02-10 1993-05-04 Toray Industries, Inc. High-tenacity water-soluble polyvinyl alcohol fiber and process for producing the same
WO2000053833A1 (de) * 1999-03-08 2000-09-14 Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Verfahren zur herstellung von formkörpern
WO2000069958A1 (en) 1999-05-18 2000-11-23 Atofina Research Reinforced polymers
FR2805179A1 (fr) 2000-02-23 2001-08-24 Centre Nat Rech Scient Procede d'obtention de fibres et de rubans macroscopiques a partir de particules colloidales, et notamment de nanotubes de carbone
WO2005061763A1 (en) * 2003-12-18 2005-07-07 The Procter & Gamble Company Rotary spinning processes for forming hydroxyl polymer-containing fibers
US7026049B2 (en) 2004-02-18 2006-04-11 Kuraray Co., Ltd. Conductive polyvinyl alcohol fiber
FR2921075A1 (fr) 2007-09-18 2009-03-20 Arkema France Procede continu d'obtention de fibres composites a base de particules colloidales et dispositif pour sa mise en oeuvre

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL142254A0 (en) * 2001-03-26 2002-03-10 Univ Ben Gurion Method for the preparation of stable suspensions of single carbon nanotubes
WO2003107359A1 (en) * 2002-06-14 2003-12-24 Hyperion Catalysis International, Inc. Electroconductive carbon fibril-based inks and coatings
WO2004024428A1 (en) * 2002-09-10 2004-03-25 The Trustees Of The University Pennsylvania Carbon nanotubes: high solids dispersions and nematic gels thereof
DE602005023616D1 (de) * 2004-07-27 2010-10-28 Dsm Ip Assets Bv Verfahren zur herstellung von verbundfasern aus kohlenstoffnanoröhren und ultrahochmolekularem polyethylen
MX2007008425A (es) * 2005-01-13 2007-12-10 Cinv Ag Materiales compuestos que contienen nanoparticulas de carbono.
US7462656B2 (en) * 2005-02-15 2008-12-09 Sabic Innovative Plastics Ip B.V. Electrically conductive compositions and method of manufacture thereof
US20070099792A1 (en) * 2005-04-27 2007-05-03 William Marsh Rice University Carbon nanotube reinforced thermoplastic polymer composites achieved through benzoyl peroxide initiated interfacial bonding to polymer matrices
US20100078194A1 (en) * 2005-08-08 2010-04-01 Sandeep Bhatt Polymeric compositions containing nanotubes
EP2477230B1 (de) * 2005-08-12 2015-02-25 Cambrios Technologies Corporation Transparente leiter auf Nanodrahtbasis auf ein flexibeler Donorsubstrat
EP1845124A1 (de) * 2006-04-14 2007-10-17 Arkema France Leitfähiger Kohlenstoff-Nanoröhren-Polymer-Verbundwerkstoff
KR101685210B1 (ko) * 2008-03-25 2016-12-09 도레이 카부시키가이샤 도전성 복합체 및 그 제조 방법
US9447251B2 (en) * 2008-07-01 2016-09-20 Vobeck Materials Corp. Articles having a compositional gradient and methods for their manufacture
US20120097903A1 (en) * 2008-12-19 2012-04-26 Vorbeck Materials Corp. Inks and coatings containing multi-chain lipids

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852402A (en) 1969-11-25 1974-12-03 S Tanaka Process for the preparation of polyvinyl alcohol fibers
US3850901A (en) 1969-11-25 1974-11-26 T Kimura Polyvinyl alcohol fibers
US4603083A (en) 1983-12-12 1986-07-29 Toray Industries, Inc. Ultra-high-tenacity polyvinyl alcohol fiber and process for producing same
US4698194A (en) 1983-12-12 1987-10-06 Toray Industries, Inc. Process for producing ultra-high-tenacity polyvinyl alcohol fiber
US4612157A (en) 1984-01-31 1986-09-16 Kuraray Company, Limited Method for production of high-tenacity, fine-denier polyvinyl alcohol fiber
WO1986003455A1 (en) 1984-12-06 1986-06-19 Hyperion Catalysis International, Inc. Carbon fibrils, method for producing same, and compositions containing same
US4971861A (en) 1986-12-27 1990-11-20 Unitika Ltd. Polyvinyl alcohol fiber and method of manufacture thereof
US5208104A (en) 1988-02-10 1993-05-04 Toray Industries, Inc. High-tenacity water-soluble polyvinyl alcohol fiber and process for producing the same
EP0395048A2 (de) * 1989-04-27 1990-10-31 Kuraray Co., Ltd. Polyvinylalkoholfaser und Verfahren zu deren Herstellung
WO2000053833A1 (de) * 1999-03-08 2000-09-14 Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Verfahren zur herstellung von formkörpern
WO2000069958A1 (en) 1999-05-18 2000-11-23 Atofina Research Reinforced polymers
US6331265B1 (en) 1999-05-18 2001-12-18 Atofina Research Reinforced polymers
FR2805179A1 (fr) 2000-02-23 2001-08-24 Centre Nat Rech Scient Procede d'obtention de fibres et de rubans macroscopiques a partir de particules colloidales, et notamment de nanotubes de carbone
WO2005061763A1 (en) * 2003-12-18 2005-07-07 The Procter & Gamble Company Rotary spinning processes for forming hydroxyl polymer-containing fibers
US7026049B2 (en) 2004-02-18 2006-04-11 Kuraray Co., Ltd. Conductive polyvinyl alcohol fiber
FR2921075A1 (fr) 2007-09-18 2009-03-20 Arkema France Procede continu d'obtention de fibres composites a base de particules colloidales et dispositif pour sa mise en oeuvre

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
B. ZHAO ET AL.: "Synthesis and Characterization of Water Soluble Single-Walled Carbon Nanotube Graft Copolymers", J. AM. CHEM. SOC., vol. 127, no. 22, 2005
XUE ET AL.: "Electrically conductive yarns based on PVA/carbon nanotubes", COMPOSITE STRUCTURES, vol. 78, 2007, pages 271 - 277
XUE ET AL: "Electrically conductive yarns based on PVA/carbon nanotubes", COMPOSITE STRUCTURES, ELSEVIER SCIENCE LTD, GB, vol. 78, no. 2, 8 December 2006 (2006-12-08), pages 271 - 277, XP005798860, ISSN: 0263-8223 *
ZHANG ET AL.: "Gel spinning of PVA/SWNT composite fiber", POLYMER, vol. 45, 2004, pages 8801 - 8807
ZHANG X ET AL: "Gel spinning of PVA/SWNT composite fiber", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 45, no. 26, 1 December 2004 (2004-12-01), pages 8801 - 8807, XP004652167, ISSN: 0032-3861 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012160288A1 (fr) 2011-05-23 2012-11-29 Arkema France Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
WO2013011250A1 (fr) * 2011-07-21 2013-01-24 Arkema France Fibres composites conductrices a base de graphene
FR2983850A1 (fr) * 2011-12-09 2013-06-14 Commissariat Energie Atomique Procede de fabrication de fibres crues et cuites a base de ceramique(s)
CN105297239A (zh) * 2015-09-17 2016-02-03 无锡市长安曙光手套厂 一种释香织物及其制备方法
CN109502570A (zh) * 2018-12-14 2019-03-22 郑州大学 导电的大应变碳纳米管复合薄膜、制备方法及测试方法

Also Published As

Publication number Publication date
FR2946177A1 (fr) 2010-12-03
JP2010281024A (ja) 2010-12-16
FR2946177B1 (fr) 2011-05-27
WO2010136704A1 (fr) 2010-12-02
CN101899723A (zh) 2010-12-01
US20110017957A1 (en) 2011-01-27
TW201111569A (en) 2011-04-01

Similar Documents

Publication Publication Date Title
EP2256236A1 (de) Verfahren zur Herstellung von leitenden Verbundfasern mit einem hohen Anteil an Nanoröhren
EP2370619B1 (de) Verbundfasern aus pekk, verfahren zur herstellung, und verwendung desselben
FR2946176A1 (fr) Fibre conductrice multicouche et son procede d'obtention par co-extrusion.
WO2010136720A1 (fr) Procede de fabrication d'une fibre conductrice multicouche par enduction-coagulation
EP2160275B1 (de) Verfahren zur imprägnierung durchgehender fasern mit einer verbundpolymermatrix mit einem gepfropften und fluorinierten polymer
RU2504604C2 (ru) Изделия из чистых углеродных нанотрубок, изготовленные из растворов суперкислот, и способы их получения
WO2013011250A1 (fr) Fibres composites conductrices a base de graphene
EP3728711A1 (de) Verfahren zur herstellung einer kohlenstofffaser aus recycelter baumwolle und verwendung der auf diese weise erhaltenen faser zur formung eines aus verbundmaterial hergestellten artikels
WO2009007617A2 (fr) Procede d'impregnation de fibres continues par une matrice polymerique composite renfermant un polymere thermoplastique
WO2009047456A2 (fr) Procede continu d ' obtention de fibres composites a base de particules colloïdales et fibre obtenue par ce procede
EP2909366A1 (de) Verfahren zur herstellung einer kohlenstofffaser, in diesem verfahren verwendetes vorläufermaterial und hergestellte kohlenstofffaser
KR101406597B1 (ko) 그래핀-고분자 수지 복합체 분말 및 섬유 제조방법
CA3039721A1 (fr) Nouveau procede de fabrication de materiaux hautement carbones et materiau hautement carbone obtenu
CA2644518C (fr) Procede de fabrication de produits extrudes composites polymeres et nanotubes de carbone
WO2012160288A1 (fr) Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
WO2019086377A2 (fr) Préparation de fibres de carbone à partir de fibres précurseurs lignine/pva
Wang et al. Fabrication and characterization of PVA/SPI/SiO2 hybrid fibres via electrospinning technique
Ranjan et al. Multi-walled carbon nanotube/polymer composite: a nano-enabled continuous fiber
Fakirov et al. From bulk polymers to nano-sized materials with controlled nanomorphology

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100520

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME RS

17Q First examination report despatched

Effective date: 20110610

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120807